CN112266455B

CN112266455B - Modified high blood-absorption polyurethane sponge, preparation method and application thereof

Info

Publication number: CN112266455B
Application number: CN202011053611.4A
Authority: CN
Inventors: 周伟琦; 尹金超; 杨晓珂; 韩洋; 田云
Original assignee: Wanhua Chemical Group Co Ltd
Current assignee: Wanhua Chemical Group Co Ltd
Priority date: 2020-09-29
Filing date: 2020-09-29
Publication date: 2022-07-12
Anticipated expiration: 2040-09-29
Also published as: CN112266455A

Abstract

The invention provides a modified high blood absorption polyurethane sponge, a preparation method and application thereof, wherein the polyurethane sponge is prepared from the following raw materials: isocyanate, polyol, super absorbent resin, fluff pulp, cationic polysaccharide, water, a hydrophilic surfactant, a chain extender, inorganic filler and an antioxidant. The polyurethane sponge prepared by the invention has the advantages of strong liquid conductivity, high utilization rate of absorption foam, strong blood absorption capacity, low blood reverse osmosis rate, low swelling rate after blood absorption and the like, can maintain higher strength after blood absorption, and is suitable for the field of disposable blood absorption sanitary products, such as sanitary towels, medical dressings and the like.

Description

Modified high blood absorption polyurethane sponge, preparation method and application thereof

Technical Field

The invention relates to the field of polyurethane foam material products, in particular to a modified high blood absorption polyurethane sponge, a preparation method and application thereof in the field of medical treatment and health.

Background

Along with the improvement of living standard of people, the using demand of people for disposable sanitary products is gradually increased, and higher requirements are put forward for the quality of the disposable sanitary products. With the industrialization of acrylic acid-based super absorbent resin, high absorbent disposable sanitary products (including feminine sanitary products, baby diapers and the like) taking super absorbent resin as filler develop rapidly, but the conventional carrier of the super absorbent resin has many problems, including uneven dispersion, easy gel blockage after liquid absorption, poor comfort and the like. Meanwhile, with diversification of user experience, people continuously demand new products. With the continuous development of polyurethane products, people find that polyurethane foam products have unique advantages (including softness, skin friendliness, strong elasticity, convenient processing and the like), so that the polyurethane foam loaded with super water-absorbent resin gradually becomes a substitute of the core body of the traditional paper diaper and the feminine hygiene product, and becomes a development direction in the future.

The invention patent CN108250402A discloses a hydrophilic soft sponge which is prepared from the following raw materials: polyether polyol, toluene diisocyanate, dichloromethane, silicone oil, water, dimethyl ethanolamine, stannous octoate, cellulose, SAP resin, porous adsorption powder subjected to surface coupling coating treatment and a nonionic surfactant. The hydrophilic soft sponge has the characteristics of softness, slow rebound, high water absorption rate, high water absorption speed and high water retention capacity, has high water absorption capacity, is not easy to dehydrate when being acted by external force, and has good water retention. However, the organic tin is used as a catalyst, the dichloromethane is used as a foaming agent, and the two chemical residues can increase the biological toxicity and influence the application of the organic tin in the field of medical treatment and health.

The invention patent CN 110577627A discloses a preparation method of an absorption material with high absorption capacity, the polyols used in the method are polyether polyols, the obtained polyurethane foam exists, the expansion is serious after blood absorption, the mechanical property is obviously reduced, and the user experience is influenced; meanwhile, the material has poor degradability, severe swelling after blood absorption and obvious reduction of mechanical properties after blood absorption.

The invention patent CN110305289A discloses non-yellowing polyurethane memory cotton and a preparation method thereof, wherein the non-yellowing polyurethane memory cotton is prepared from the following raw materials in parts by weight: 50-80 parts of high-activity polyether polyol, 5-40 parts of slow-rebound polyether, 2-35 parts of polymer polyol, 1-10 parts of chain extender, 0.2-3 parts of foam stabilizer, 0.5-3 parts of composite catalyst, 1-4 parts of water and 30-60 parts of aliphatic isocyanate. The liquid transfer agent mainly solves the problems of yellowing resistance and slow rebound, but has different application fields, and does not disclose how to improve the performances in the aspects of liquid transfer, blood absorption and the like.

Nevertheless, polyurethane foams still have some problems, which greatly affect the application range of the polyurethane foams in the disposable sanitary product industry, and bring poor consumption experience to consumers. The main problems include the following:

1) polyurethane foam absorbers have some inherent absorption disadvantages. The porosity is large, the absorption performance is poor, the gravity cannot be overcome to effectively distribute fluid, the liquid permeability of foam is poor, the absorption utilization rate is low, and the absorption effect is poor. Secondly, excessive fluid limitation interacts with SAP particles and soft segments of polyoxyethylene segments, so that local expansion is serious after the fluid is absorbed, the strength is reduced quickly, and the application and popularization of the composite material in the field of sanitary products are influenced.

2) The SAP-containing polyurethane foam has poor absorption of blood. The conventional SAP-containing polyurethane high-absorption foam can effectively absorb simple fluids such as water, urine and the like, but blood is complex fluid, and the complex fluid contains dissolved organic matters such as blood cells and proteins, metal ions and the like; the blood cells and the proteins can cause high fluid viscosity, and cover the surface of the absorbent body after being absorbed to inhibit the further absorption of blood; the metal ions and the surface of the absorber generate coordination, so that the absorber loses absorption capacity, the ability of the foam absorber for absorbing and storing blood is greatly influenced, and low utilization rate and poor use feeling are caused.

Therefore, the liquid guiding performance of the polyurethane foam absorber is improved, the absorption and storage capacity of the foam absorber to blood is improved, the utilization rate of the polyurethane foam disposable hygienic product is improved, the actual liquid absorption amount is increased, the raw material utilization amount is favorably reduced, the cost is saved, and the development of the hygienic product towards diversification, high efficiency, comfort and light weight is favorably promoted.

Disclosure of Invention

The invention aims to overcome the defects of the prior art, and provides a modified high blood absorption polyurethane sponge on the premise of not changing the advantages of softness, skin friendliness, convenient preparation, good SAP dispersing effect and the like of polyurethane foam, so that the drainage property, the blood absorption utilization rate and the specific blood absorption capacity of the sponge are improved, and the swelling rate of the sponge is reduced.

The invention also aims to provide a preparation method of the modified high blood absorption polyurethane sponge.

It is a further object of the present invention to provide the use of such modified high blood-absorbing polyurethane sponges.

In order to realize the purpose, the invention adopts the following technical scheme:

a modified high blood absorption polyurethane sponge is prepared from the following raw materials in parts by weight: 20-40 parts of isocyanate, 60-120 parts of polyol, 10-30 parts of fluff pulp fiber, 20-50 parts of super absorbent resin, 5-20 parts of cationic polysaccharide, 60-100 parts of water, 1-10 parts of hydrophilic surfactant, 1-3 parts of chain extender, 10-30 parts of inorganic filler and 0.1-0.5 part of antioxidant.

In a preferred embodiment, the composition is prepared from the following raw materials in parts by weight: 25-35 parts of isocyanate, 80-110 parts of polyol, 10-30 parts of fluff pulp fiber, 25-40 parts of super absorbent resin, 5-10 parts of cationic polysaccharide, 80-100 parts of water, 2-8 parts of hydrophilic surfactant, 1-3 parts of chain extender, 15-25 parts of inorganic filler and 0.2-0.4 part of antioxidant.

Wherein the isocyanate is selected from any one or more of diphenylmethane diisocyanate (MDI), Toluene Diisocyanate (TDI), dicyclohexylmethane diisocyanate (HMDI), Hexamethylene Diisocyanate (HDI) and isophorone diisocyanate (IPDI).

Wherein, the polyol is selected from one or a mixture of more of polyester polyol and polyether polyol; preferably, the polyester polyol has a functionality of 2 to 4 and a molecular weight of 1000-; the polyether polyol has the functionality of 2-3 and the molecular weight of 300-5000; more preferably, the polyester polyol is selected from at least one of polylactic acid polyol, polyglycolide polyol and polyethylene-propylene-glycol-co-polyester polyol, and the polyether polyol is selected from any one or more of polyethylene glycol, polypropylene glycol and ethylene glycol-propylene glycol co-polyester polyol.

Wherein, the fluff pulp fiber is the fluff pulp fiber with high whiteness, high conduction and high absorption speed; preferably, the fluff pulp fiber is the fluff pulp with the whiteness of more than or equal to 90 and the water absorption time of less than or equal to 0.4 s.

Wherein, the super absorbent resin is acrylic acid-based super absorbent resin, and the particle size range is 100-700 μm, preferably 100-300 μm.

Wherein the cationic polysaccharide is selected from one or more of chitosan, polyquaternium-10, polyquaternium-4, polyquaternium-24, polyquaternium-67 and guar hydroxypropyl trimonium chloride.

Wherein the hydrophilic surfactant is a nonionic surfactant; preferably, the polyether is selected from one or more of fatty alcohol polyoxyethylene ether, polyoxyethylene fatty acid ester, EO/PO block polyether, polyglycerol fatty acid ester, castor oil polyoxyethylene ether, straight-chain isooctanol polyoxyethylene ether, polyoxyethylene alkyl ether and sorbitol fatty acid ester.

Wherein, the inorganic filler is selected from one or more of calcium carbonate, zinc oxide, montmorillonite, diatomite, kaolin and titanium dioxide; preferably, the particle size of the inorganic filler is 300-800 mesh.

In another aspect of the present invention, the preparation method of the modified high blood absorption polyurethane sponge comprises the following steps:

s1, preparing a prepolymer: reacting the isocyanate, the polyol, the chain extender and the antioxidant in parts by weight for 10-12 hours at the temperature of 60-80 ℃ to obtain a prepolymer;

s2, adding the super absorbent resin in parts by weight into the prepolymer obtained in the step S1, and uniformly dispersing to obtain a material B;

s3, dispersing the fluff pulp fibers, the cationic polysaccharide, the hydrophilic surfactant and the inorganic filler in water in parts by weight to obtain a material A;

and S4, mixing the material B and the material A under the condition of high-speed stirring, and foaming by adopting a manual method or a foaming agent to prepare the high blood absorption polyurethane sponge.

In still another aspect of the present invention, the use of the modified high blood absorption polyurethane sponge is used in the field of disposable absorbent articles, preferably in the field of disposable blood absorption sanitary articles, and more preferably used as sanitary napkins and medical dressings.

Compared with the prior art, the invention has the following beneficial effects:

(1) according to the invention, the mechanical property of the absorber sponge is adjusted by adjusting the types and the proportion of the polyester polyol and the polyether polyol in the soft segment, the processing mode is optimized, more comfortable use experience is brought to consumers, and the degradability of the absorber sponge can be effectively adjusted and the moisture absorption of the sponge is adjusted by introducing the polylactic acid polyol, so that the problems of storage of the sponge absorber and white pollution are solved.

(2) According to the invention, after the cationic polysaccharide is introduced into the sponge absorber, the cationic polysaccharide can effectively interact with blood cells with negative electricity by virtue of the gelation effect and the self negative electricity effect of the cationic polysaccharide, proteins and the blood cells are fixed by gelation, the gel simultaneously adsorbs and chelates most of metal ions in blood, the reduction of the absorption capacity of PEG (polyethylene glycol) areas and SAP (super absorbent polymer) particles on the blood caused by surface adhesion is reduced, and the blood absorption capacity of the sponge absorber is improved.

(3) The addition of cationic polysaccharides in the sponge absorbent body of the present invention also provides other additional effects: 1) the foaming speed is increased, the problem that the aliphatic isocyanate is slow to foam is solved, and the aliphatic isocyanate can endow the sponge absorber with the characteristic of yellowing resistance; 2) the high molecular cross-linking agent improves the mechanical strength of the sponge absorber; 3) the cation has certain antibacterial performance, and an antibacterial agent is not required to be added into the material; 4) compared with the traditional micromolecular surfactant, the cationic polysaccharide has high binding force with the sponge absorber, is not easy to dissolve out, and increases the biological safety of the sponge absorber.

(4) According to the invention, the fluff pulp fibers are introduced into the sponge absorber, and the fluff pulp has a fast absorption effect and a strong conduction effect on liquid, so that the fluid can be rapidly distributed, the defect that the polyurethane sponge absorber cannot effectively distribute the fluid by gravity due to large pores is solved, the actual utilization efficiency of the sponge absorber is improved, and the deformation problem after absorption is relieved to a certain extent; secondly, the fluff pulp is cellulose material, the surface of which contains abundant hydroxyl groups, the hydroxyl groups can react with isocyanate, and more 'polar micro-regions' can be generated in the material, so that the strength of the material is increased.

(5) The polyurethane sponge absorber prepared by the invention has the advantages of high blood absorption amount, strong liquid guiding property, low reverse osmosis after absorption, no deformation after blood absorption of the sponge absorber, and wide application prospect in the field of medical treatment and health.

Drawings

FIG. 1 is a graph showing the effect of blood absorption, expansion and diffusion in comparative example 2 and example 7 of the present invention after 5ml of blood injection.

Detailed Description

The following examples will further illustrate the method provided by the present invention in order to better understand the technical solution of the present invention, but the present invention is not limited to the listed examples, and should also include any other known modifications within the scope of the claims of the present invention.

In a more preferred embodiment, the composition is prepared from the following raw materials in parts by weight: 25-35 parts of isocyanate, 80-110 parts of polyol, 10-30 parts of fluff pulp fiber, 25-40 parts of super absorbent resin, 5-10 parts of cationic polysaccharide, 80-100 parts of water, 2-8 parts of hydrophilic surfactant, 1-3 parts of chain extender, 15-25 parts of inorganic filler and 0.2-0.4 part of antioxidant.

The isocyanate may be selected from any one or a mixture of several of diphenylmethane diisocyanate (MDI), Toluene Diisocyanate (TDI), dicyclohexylmethane diisocyanate (HMDI), Hexamethylene Diisocyanate (HDI), and isophorone diisocyanate (IPDI). Such as, but not limited to, MDI or TDI, or 60% MDI and 40% TDI, or 40% TDI and 60% MDI, but also other NCO group-containing isocyanates, which are primarily used as the primary raw material for polyurethane foams, react to form a foam structure.

The polyol may be a polyester polyol or a polyether polyol, or may be a mixture of both. Wherein, the functionality of the polyester polyol is 2-4, the molecular weight is 1000-4000, for example, at least one selected from polylactic acid polyol, polyglycolide polyol and polyethylene-propylene-diene-terpolymer polyol, preferably polylactic acid polyol. The polyether polyol has a functionality of 2-3 and a molecular weight of 300-4000, and is selected from any one or more of polyethylene glycol, polypropylene glycol, ethylene glycol and propylene glycol copolymer. Through the selection of two types of polyols and the compounding of the weights, firstly, the interaction between the product and the aqueous liquid is adjusted; secondly, the degradability of the product is adjusted.

The super absorbent resin is, for example, an acrylic acid-based super absorbent resin, and the particle size range thereof is between 100-700 microns, preferably 100-300 microns. The super absorbent resin particles with lower particle size can have larger contact area and faster liquid absorption rate, and are more suitable for the product system, but if the particle size is too small, the viscosity of the system can be increased, and the foaming difficulty can be increased. Specifically, a commercial super absorbent resin SAP such as at least one of sumitomo 60N, WHS 300, WHS 736, WSJ, NR 860 is preferable.

As the fluff pulp fibers, for example, high-whiteness, high-conductivity, high-suction-rate fluff pulp fibers; specifically, the preferred fluff pulp fiber is fluff pulp with whiteness not less than 90 and water absorption time not more than 0.4 s.

The cationic polysaccharide is, for example, at least one selected from the group consisting of chitosan, polyquaternium-10, polyquaternium-4, polyquaternium-24, polyquaternium-67, and guar hydroxypropyltrimonium chloride, and preferably at least one selected from the group consisting of chitosan and polyquaternium-10.

The hydrophilic surfactant is, for example, a nonionic surfactant, specifically, one or more selected from fatty alcohol-polyoxyethylene ether, polyoxyethylene fatty acid ester, EO/PO block polyether, polyglycerol fatty acid ester, castor oil polyoxyethylene ether, linear octa isooctanol polyoxyethylene ether, polyoxyethylene alkyl ether, and sorbitol fatty acid ester, preferably at least one selected from EO/PO block polyether and fatty alcohol-polyoxyethylene ether, and is added mainly for adjusting the hydrophilicity and hydrophobicity of the product and stabilizing the structure of the polyurethane foam itself.

The chain extender is any one or a mixture of glycerol, diethanolamine, triethanolamine, trimethylolpropane and pentaerythritol, preferably glycerol or trimethylolpropane, but is not limited thereto, and other chain extenders commonly used in the polyurethane technology field can be used, and simple substitution thereof is also within the protection scope of the present invention.

The inorganic filler is selected from any one of calcium carbonate ultrafine powder, bentonite, kaolin, montmorillonite, diatomite, zinc oxide, titanium dioxide and the like or a mixture thereof, preferably at least one of diatomite or bentonite, and the particle size of the inorganic filler is 300 meshes-800 meshes. The addition of proper inorganic filler can further improve the connectivity, hydrophilicity and hardness among cells and further improve various indexes of the product.

The antioxidant is, for example, a commercially available complex antioxidant, and specifically includes any one or a mixture of IRGANOX 1010, IRGANOX 1035, IRGANOX B1411, IRGANOX B1412, IRGANOX PS800, IRGANOX PS802, IRGAFOS P-EPQ, IRGASTAB PUR 55, IRGASTAB PUR 68, and IRGASTAB PUR 70 from BASF, Germany.

The modified high blood absorption polyurethane sponge is prepared by mixing and foaming the components in parts by weight according to the following preparation method, and specifically comprises the following steps:

s1, preparing a prepolymer: reacting isocyanate, polyalcohol, a chain extender and an antioxidant at the temperature of 60-80 ℃ for 8-12h to obtain a prepolymer;

s2, adding the super absorbent resin into the prepolymer to be uniformly dispersed to obtain a material B;

s3, dispersing a hydrophilic surfactant, fluff pulp fibers and an inorganic filler in water to obtain a material A;

and S4, mixing the material B and the material A under the condition of high-speed stirring, and foaming by adopting a manual method or a foaming agent to obtain the modified high blood absorption polyurethane sponge.

The high-speed stirring condition in step S4, for example, the stirring speed is 3000-5000rpm, and the uniform mixing of the materials A and B can be realized by stirring for 10-15S. The foaming process may be a conventional foaming process in the polyurethane field, for example, refer to patent CN 110577627 a.

The process for the preparation of the polyurethane sponges according to the invention is further illustrated below by means of several more specific examples, which are given only by way of illustration and are not intended to limit the invention in any way.

Material source:

isocyanate: toluene Diisocyanate (TDI)

TDI-80 with purity not less than 99.6%; hexamethylene isocyanate:

HDI, purity not less than 99.6% (Wanhua chemical)

Polyether polyol: PEG-2000, functionality 2 (Haian petrochemical)

Fluff pulp: 481 grade fluff pulp (Huihao), whiteness not less than 90, and water absorption time not more than 0.4s

Super absorbent resin: an acrylic acid-based super absorbent resin,

300 (Wanhua chemical)

Cationic polysaccharide: chitosan, viscosity 100-

Polyquaternary ammonium-10 (Tianjin xi Ensi)

Hydrophilic surfactant:

188 nonionic surfactant, EO/PO block copolymer (BASF);

PE6400(BASF)

chain extender: trimethylolpropane (TMP), 98%, (Aladdin chemical)

Antioxidant: IRGASTAB PUR 68, (BASF)

Inorganic filler: the diatomite standard has a mesh size of 300 meshes (Imercy)

The polylactic acid dihydric alcohol is synthesized by the following method:

heating the dehydrated lactic acid and 1, 4-butanediol to 140 ℃ for pre-esterification for 4 hours, vacuumizing to suck away unreacted small molecules, adding 0.4% of zinc-bismuth composite catalyst, heating to 180 ℃ and reacting for 8 hours to obtain polylactic acid dihydric alcohol with the hydroxyl value of 39 and the molecular weight of about 3000.

The performance test of the high blood absorption polyurethane sponge prepared by the invention adopts the following method:

1) blood absorption properties (reverse osmosis, diffusion length, deformation, blood uptake rate):

the method and standard for testing blood absorption performance refer to the contents in the paper diaper (sheet, pad) standard GB/T28004 & 2011 and the sanitary napkin (pad) standard GB/T28004 & 2011, and are modified and adjusted appropriately as follows:

cutting the disposable sponges obtained in the examples and the comparative examples into long-piece samples with the length of 200mm, the width of 80mm and the thickness of 2 mm; replacing the composite absorbent core of a commercially available sanitary napkin with the long sheet obtained in examples and comparative examples, and referring to the procedure of the sanitary napkin test method, adding thereto swine blood dropwise, starting from the moment when the blood contacts the surface until the moment when the liquid completely disappears, and recording the time elapsed for the first blood absorption as the blood absorption rate; standing for five minutes, pressing the filter paper with a 2.5kg weight for 2 minutes, testing the weight gain of the filter paper, repeating for three times, and adding the weight gains of the filter paper for three times to obtain the reverse osmosis value of the sponge sanitary product; and simultaneously observing the deformation condition of the sanitary product after blood suction, measuring the diffusion length of the polyurethane sanitary product by using a vernier caliper after the test is finished, and observing the deformation quantity of the foamed plastic.

2) Flexibility:

the softness test method adopts a qualitative comparison method, selects an evaluation group of 12 persons, and adopts a method of directly touching and pulling by hands to test the softness and tensile strength of the sponge.

3) Water absorption rate:

the method for measuring the water absorption capacity and the standard refer to the test part of the water absorption capacity in the paper diaper and the super absorbent resin for sanitary towel GB/T22875-2018, and the appropriate modification and adjustment are carried out. Specifically, the disposable sponges obtained in the examples and the comparative examples are cut into sheet samples with the length of 40mm, the width of 40mm and the thickness of 2mm according to the size, the initial weight m of the samples is recorded, the samples are soaked in salt water for 30min, and then the mass m is recorded after the samples are hung and aired for 10min₁And calculating the final water absorption multiplying power by the following formula:

the invention is further illustrated by the following more specific examples, without restricting it in any way.

Example 1

A. Weighing the following components in parts by weight: a modified high blood absorption polyurethane sponge is prepared from the following raw materials in parts by weight: 30 parts of isocyanate, wherein the mass ratio of methyl isocyanate to hexamethylene isocyanate is 6: 4, 18 parts of polylactic acid dihydric alcohol, 15 parts of fluff pulp, 15 parts of PEG-200042 parts of super absorbent resin WHS 30030 parts of chitosan, 90 parts of water and (hydrophilic surfactant) ((

PE6400：

188 ═ 1: 2)5 parts of chain extender TMP 2 parts, inorganic filler 300-mesh diatomite 20 parts, antioxidant IRGASTAB PUR 680.3 parts;

B. isocyanate, polyether polyol, polyester polyol, polymer polyol, a chain extender and an antioxidant are placed at 80 ℃ for reaction for 12 hours to obtain a polyol modified prepolymer;

C. uniformly mixing fluff pulp fibers, chitosan, a hydrophilic surfactant, an inorganic filler and water to obtain a white material, and keeping the white material at 20 +/-2 ℃;

D. heating the prepolymer to 40 ℃, then uniformly mixing the super absorbent resin and the modified prepolymer at 1500rpm, stirring the mixture and the white material at the rotation speed of 4000rpm for 10s, placing the mixture in a foaming box for foaming, and recording the foaming time;

E. curing for 36h in an environment of 50 ℃, and cutting to obtain the disposable polyurethane sponge.

The product prepared by the method of the embodiment has low blood swelling ratio, low blood reverse osmosis and good degradability.

Example 2

A. Weighing the following components in parts by weight: a modified high blood absorption polyurethane sponge is prepared from the following raw materials in parts by weight: 30 parts of isocyanate, wherein the ratio of methyl isocyanate to hexamethylene isocyanate is 6: 4, 36 parts of polylactic acid dihydric alcohol, 15 parts of fluff pulp, 15 parts of PEG-200084 parts of super absorbent resin WHS 30030 parts of chitosan, 90 parts of water and hydrophilic surfactant(s) ((

PE6400：

188 is 1: 2)5 parts of chain extender TMP 2 parts, 20 parts of inorganic filler diatomite with 300 meshes and 680.3 parts of antioxidant IRGASTAB PUR;

D. heating the prepolymer to 40 ℃, then uniformly mixing the super absorbent resin and the modified prepolymer at 1500rpm, stirring the mixture and the white material at 4000rpm for 10s, placing the mixture in a foaming box for foaming, and recording the foaming time;

E. and curing for 36 hours in an environment of 50 ℃, and cutting to obtain the disposable polyurethane sponge.

The product prepared by the method of the embodiment has low blood swelling rate, low blood reverse osmosis and good degradability.

Example 3

A. Weighing the following components in parts by weight: a modified high blood absorption polyurethane sponge is prepared from the following raw materials in parts by weight: 30 parts of isocyanate, wherein the ratio of methyl isocyanate to hexamethylene isocyanate is 6: 4, 30 parts of polylactic acid dihydric alcohol, 15 parts of PEG-200070, 15 parts of fluff pulp, 30 parts of super absorbent resin WHS 30030, 15 parts of chitosan, 90 parts of water and hydrophilic surfactant(s) ((R))

PE6400：

Example 4

A. Weighing the following components in parts by weight: a modified high blood absorption polyurethane sponge is prepared from the following raw materials in parts by weight: 30 parts of isocyanate, wherein the ratio of methyl isocyanate to hexamethylene isocyanate is 6: 4, 10 parts of fluff pulp, 30 parts of polylactic acid dihydric alcohol, PEG-200070 parts, 30 parts of super absorbent resin WHS 30030 parts, 5 parts of chitosan, 90 parts of water, and a hydrophilic surfactant (a: (a) hydrophilic surfactant

PE6400：

Example 5

A. Weighing the following components in parts by weight: a modified high blood absorption polyurethane sponge is prepared from the following raw materials in parts by weight: 30 parts of isocyanate, wherein the ratio of methyl isocyanate to hexamethylene isocyanate is 6: 4, 20 parts of fluff pulp, 30 parts of polylactic acid dihydric alcohol, PEG-200070 parts, super absorbent resin WHS 30040 parts, deethyl5 parts of acyl chitosan, 90 parts of water, and (a) hydrophilic surfactant

PE6400：

188 ═ 1: 2)5 parts of chain extender TMP 2 parts, 20 parts of inorganic filler diatomite with 300 meshes and 680.3 parts of antioxidant IRGASTAB PUR;

Example 6

A. Weighing the following components in parts by weight: a modified high blood absorption polyurethane sponge is prepared from the following raw materials in parts by weight: 30 parts of isocyanate, wherein the ratio of methyl isocyanate to hexamethylene isocyanate is 6: 4, 30 parts of fluff pulp, 30 parts of polylactic acid dihydric alcohol, PEG-200070 parts, 30 parts of super absorbent resin WHS 30030 parts, 5 parts of chitosan, 90 parts of water and hydrophilic surfactant(s) ((R))

PE6400：

Example 7

A. Weighing the following components in parts by weight: a modified high blood absorption polyurethane sponge is prepared from the following raw materials in parts by weight: 30 parts of isocyanate, wherein the ratio of methyl isocyanate to hexamethylene isocyanate is 6: 4, 15 parts of fluff pulp, 30 parts of polylactic acid dihydric alcohol, PEG-200070 parts, 30 parts of super absorbent resin WHS 30030 parts, 5 parts of chitosan, 90 parts of water and hydrophilic surfactant(s) ((R))

PE6400：

188 is 1: 2)5 parts of chain extender TMP 2 parts, inorganic filler 300-mesh diatomite 20 parts, antioxidant IRGASTAB PUR 680.3 parts;

B. placing isocyanate, polyether polyol, polyester polyol, polymer polyol, a chain extender and an antioxidant at 80 ℃ for reaction for 12 hours to obtain a polyol modified prepolymer;

Example 8

A. Weighing the following components in parts by weight: a modified high blood absorption polyurethane sponge is prepared from the following raw materials in parts by weight: 30 parts of isocyanate, wherein the ratio of methyl isocyanate to hexamethylene isocyanate is 6: 4, 15 parts of fluff pulp, 30 parts of polylactic acid dihydric alcohol, PEG-200070 parts, 30 parts of super absorbent resin WHS 30030 parts, 10 parts of chitosan, 90 parts of water and hydrophilic surfactant(s) ((R))

PE6400：

Example 9

A. Weighing the following components in parts by weight: a modified high blood absorption polyurethane sponge is prepared from the following raw materials in parts by weight: 30 parts of isocyanate, wherein the ratio of methyl isocyanate to hexamethylene isocyanate is 6: 4, 15 parts of fluff pulp, PEG-2000100 parts, 30 parts of super absorbent resin WHS 30010 parts of chitosan, 90 parts of water, hydrophilic surfactant(s) ((R))

PE6400：

Example 10

A. Weighing the following components in parts by weight: a modified high blood-absorption polyurethane sponge is prepared from the following raw materials in parts by weightThe composition is as follows: 30 parts of isocyanate, wherein the ratio of methyl isocyanate to hexamethylene isocyanate is 6: 4, 30 parts of polylactic acid dihydric alcohol, 30 parts of PEG-200070 parts of super absorbent resin WHS 30030 parts of polyquaternium-105 parts of water, 90 parts of hydrophilic surfactant (i)

PE6400：

Example 11

A. Weighing the following components in parts by weight: a modified high blood absorption polyurethane sponge is prepared from the following raw materials in parts by weight: 30 parts of isocyanate, wherein the ratio of methyl isocyanate to hexamethylene isocyanate is 6: 4, 15 parts of fluff pulp, 50 parts of polylactic acid dihydric alcohol, PEG-200050 parts, high water-absorbing resin WHS 30030 parts, 5 parts of chitosan, 90 parts of water, and a hydrophilic surfactant (A)

PE6400：

Comparative example 1

A. Weighing the following components in parts by weight: a high-absorption polyurethane disposable sponge is prepared from the following raw materials in parts by weight: 30 parts of isocyanate, wherein the ratio of methyl isocyanate to hexamethylene isocyanate is 6: 4, 30 parts of polylactic acid polyol, 30 parts of PEG-200070, 30 parts of super absorbent resin, 5 parts of chitosan, 90 parts of water, 5 parts of hydrophilic surfactant, 2 parts of chain extender, 20 parts of inorganic filler and 0.3 part of antioxidant, and the foaming method refers to the method in example 1 for foaming.

Comparative example 2

A. Weighing the following components in parts by weight: a high-absorption polyurethane disposable sponge is prepared from the following raw materials in parts by weight: 30 parts of isocyanate, wherein the ratio of methyl isocyanate to hexamethylene isocyanate is 6: 4, 30 parts of polylactic acid polyol, 30 parts of PEG-200070, 30 parts of super absorbent resin, 90 parts of water, 5 parts of hydrophilic surfactant, 2 parts of chain extender, 20 parts of inorganic filler and 0.3 part of antioxidant, and the foaming method refers to the method in example 1 for foaming.

Comparative example 3

A. Weighing the following components in parts by weight: a high-absorption polyurethane disposable sponge is prepared from the following raw materials in parts by weight: 30 parts of isocyanate, wherein the ratio of methyl isocyanate to hexamethylene isocyanate is 6: 30 parts of polylactic acid polyol, 15 parts of fluff pulp, PEG-200070 parts, 30 parts of super absorbent resin, 90 parts of water, 5 parts of hydrophilic surfactant, 2 parts of chain extender, 20 parts of inorganic filler and 0.3 part of antioxidant, and the foaming method refers to the method in example 1 for foaming.

The main reaction conditions and product performance test results of the inventive examples and comparative examples are shown in table 1.

TABLE 1 main reaction conditions and product Performance test results of examples and comparative examples

Item	Example 1	Example 2	Example 3	Example 4	Example 5	Example 6	Example 7	Example 8	Example 9	Example 10	Example 11	Comparative example 1	Comparative example 2	Comparative example 3
															Isocyanates	30	30	30	30	30	30	30	30	30	30	30	30	30	30
Super absorbent resin	30	30	30	30	40	30	30	30	30	30	30	30	30	30
															Water (W)	90	90	90	90	90	90	90	90	90	90	90	90	90	90
Hydrophilic surfactant	5	5	5	5	5	5	5	5	5	5	5	5	5	5
															Chain extender	2	2	2	2	2	2	2	2	2	2	2	2	2	2
Inorganic filler	20	20	20	20	20	20	20	20	20	20	20	20	20	20
															Antioxidant agent	0.3	0.3	0.3	0.3	0.3	0.3	0.3	0.3	0.3	0.3	0.3	0.3	0.3	0.3
Polyester polyol: PEG	18/42	36/84	30/70	30/70	30/70	30/70	30/70	30/70	0/100	30/70	50/50	30/70	30/70	30/70
															Fluff pulp	15	15	15	10	20	30	15	15	15	15	15	0	0	15
Cationic polysaccharides	5	5	15	5	5	5	5	10	5	5	5	5	0	0
															Reverse osmosis per gram	6.3	5.7	4.7	6.1	5.3	4.8	5.5	4.9	6.8	5.2	7.3	7.6	9.6	8.4
Deformation of	It is excellent in	Good effect	Is excellent in	Is excellent in	It is excellent in	Is excellent in	Is excellent in	Is excellent in	In general	Is excellent in	Is excellent in	In general	Is poor	Is excellent in
															Comfort level	In general	Is soft and flexible	In general	Softness	Softness	Softness	Softness	Softness	Softness	Softness	Hard	Softness	Is soft and flexible	Softness
Diffusion length/cm	11.6	11.2	12.9	10.8	12.3	13.1	12.1	12.5	11.2	12.8	12.9	9.2	8.6	9.8
															Blood suction speed/s	18	8	9	10	8	7	8	8	8	9	16	13	25	12
Water absorption rate	12.1	14.9	13.6	13.5	13.8	13.4	13.5	13.2	15.2	13.4	11.2	13.7	12.6	12.9
															Foaming time/s	105	125	39	111	113	118	115	75	108	112	126	109	172	168

As can be seen from the data in the above table, the effect of different addition amounts of polyol on the product performance can be seen in examples 1, 2 and 7, the change of the polyol content indirectly changes the NCO content of isocyanate and the foam performance, and as the polyol content increases, the softness and water absorption rate of the sponge increase but the deformation performance thereof decreases. Compared with the comparative example 1 and the examples 4, 5, 6 and 7, the doping of the fluff pulp fibers can increase the liquid conductivity of the sponge, improve the utilization rate of the sponge, reduce the reverse osmosis amount and reduce the deformation, and the longer the diffusion length is, the better the liquid conductivity is, so that more sponge absorbs liquid and the higher the utilization rate of the sponge is; however, since too much fluff pulp fibers are mixed, which causes uneven stirring and makes processing difficult, it is necessary to adjust the mixing amount of the fluff pulp fibers appropriately. Examples 3, 7, 8, 10 and comparative example 3 show that the addition of the cationic polysaccharide effectively enhances the blood absorption speed of the polyurethane sponge through the charge effect and the gel effect thereof, and effectively reduces the blood reverse osmosis, which is an important performance index of the sanitary product, and the lower the reverse osmosis, the more helpful the dryness of the sanitary product is to be maintained; meanwhile, the foaming speed of the polyurethane sponge is accelerated by the cationic polysaccharide, probably because the self amino group of the chitosan or the quaternary ammonium salt group of polyquaternium-10 plays a role in catalyzing the reaction, but the excessive addition of the cationic polysaccharide causes the excessively high reaction speed, so that the difficulty in material production is multiplied, and the addition amount is reasonably adjusted. From examples 7, 9 and 11, the proper ratio of polylactic acid polyol and PEG can adjust the strength, hydrophilicity, liquid retention property and absorption speed of the sponge, increase the distribution efficiency of blood by adding proper amount of polylactic acid polyol, prevent the low utilization rate of the sponge caused by blood aggregation and reduce reverse osmosis; meanwhile, the strength of the sponge product can be properly adjusted.

In addition, the products obtained in example 7 and comparative example 2 were subjected to blood absorption swelling and diffusion experiments, and the blood absorption swelling and diffusion effects were observed after 5min after 5ml blood injection, as shown in fig. 1, the left side is comparative example 2, which shows a small diffusion swelling, and the right side is inventive example 7, which shows a long diffusion and no swelling. The polyurethane sponge prepared by the method has good liquid conductivity and low blood swelling rate.

In addition, the polylactic acid polyol is easily degradable and high in biosafety, and the biodegradability of the disposable sponge can be greatly improved by adding the polylactic acid polyol. The high blood absorption polyurethane sponge prepared by the components and the method has good liquid permeability, high absorption speed, low blood swelling rate, low blood reverse osmosis and even good degradability, can be used in the field of disposable absorption products, is particularly suitable for the field of disposable blood absorption sanitary products, and is more preferably used as sanitary towels and medical dressings.

While the present invention has been described in detail with reference to the preferred embodiments, it should be understood that the above description should not be taken as limiting the invention. It will be appreciated by those skilled in the art that modifications or adaptations to the invention may be made in light of the teachings of the present specification. Such modifications or adaptations are intended to be within the scope of the present invention as defined in the claims.

Claims

1. The modified high blood absorption polyurethane sponge is characterized by being prepared from the following raw materials in parts by weight: 20-40 parts of isocyanate, 60-120 parts of polyol, 10-30 parts of fluff pulp fiber, 20-50 parts of super absorbent resin, 5-20 parts of cationic polysaccharide, 60-100 parts of water, 1-10 parts of hydrophilic surfactant, 1-3 parts of chain extender, 10-30 parts of inorganic filler and 0.1-0.5 part of antioxidant;

the polyol is selected from one or a mixture of polyester polyol and polyether polyol;

the cationic polysaccharide is selected from one or more of chitosan, polyquaternium-10, polyquaternium-4, polyquaternium-24, polyquaternium-67 and guar hydroxypropyl trimonium chloride.

2. The modified high blood-absorption polyurethane sponge according to claim 1, which is prepared from the following raw materials in parts by weight: 25-35 parts of isocyanate, 80-110 parts of polyol, 10-30 parts of fluff pulp fiber, 25-40 parts of super absorbent resin, 5-10 parts of cationic polysaccharide, 80-100 parts of water, 2-8 parts of hydrophilic surfactant, 1-3 parts of chain extender, 15-25 parts of inorganic filler and 0.2-0.4 part of antioxidant.

3. The modified Haemophilus spongia according to claim 1 or 2, wherein the isocyanate is selected from any one or more of diphenylmethane diisocyanate, toluene diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate.

4. The modified high blood absorption polyurethane sponge as claimed in claim 1, wherein the polyester polyol has a functionality of 2-4 and a molecular weight of 1000-4000; the polyether polyol has a functionality of 2-3 and a molecular weight of 300-5000.

5. The modified high blood absorption polyurethane sponge according to claim 4, wherein the polyester polyol is at least one selected from polylactic acid polyol, polyglycolide polyol and polyethylene-propylene-glycol-lactide polyol, and the polyether polyol is any one or more selected from polyethylene glycol, polypropylene glycol and ethylene-propylene glycol copolymer polyol.

6. The modified high blood absorption polyurethane sponge according to claim 1 or 2, wherein the fluff pulp fibers are fluff pulp with whiteness not less than 90 and water absorption time not more than 0.4 s.

7. The modified high blood absorption polyurethane sponge according to claim 1 or 2, wherein the high water absorption resin is acrylic acid-based high water absorption resin, and the particle size range is 100-700 μm.

8. The modified high blood absorption polyurethane sponge according to claim 7, wherein the particle size of the high water absorption resin is in the range of 100-300 μm.

9. The modified hyperphagia polyurethane sponge according to claim 1 or 2, wherein the hydrophilic surfactant is a nonionic surfactant.

10. The modified high blood absorption polyurethane sponge according to claim 9, wherein the hydrophilic surfactant is selected from one or more of fatty alcohol polyoxyethylene ether, polyoxyethylene fatty acid ester, EO/PO block polyether, polyglycerol fatty acid ester, castor oil polyoxyethylene ether, polyoxyethylene alkyl ether and sorbitol fatty acid ester.

11. The modified high blood absorption polyurethane sponge according to claim 1 or 2, wherein the inorganic filler is selected from one or more of calcium carbonate, zinc oxide, montmorillonite, diatomite, kaolin and titanium dioxide.

12. The modified high blood absorption polyurethane sponge according to claim 11, wherein the particle size of the inorganic filler is 300-800 mesh.

13. A process for preparing a modified high blood absorption polyurethane sponge according to any one of claims 1 to 12, comprising the steps of:

s3, dispersing the fluff pulp fibers, the cationic polysaccharide, the hydrophilic surfactant and the inorganic filler in parts by weight in water to obtain a material A;

and S4, mixing the material B and the material A under the condition of high-speed stirring, and foaming by adopting a manual or foaming agent to prepare the high blood-absorption polyurethane sponge.

14. Use of the modified high blood-absorption polyurethane sponge according to any one of claims 1 to 12 in the field of disposable absorbent articles.

15. Use of the modified high blood absorption polyurethane sponge of claim 14 in the field of disposable blood absorption sanitary products.

16. Use of the modified high blood-absorbing polyurethane sponge of claim 15 as a sanitary napkin, medical dressing.